JPH04239569A - Water-base marking pen ink for writing board - Google Patents

Abstract

PURPOSE:To provide a water-base marking pen ink for writing on an ink- impermeable writing board to give a written mark cleanly erasable without staining the board surface by rubbing with a dry erasing material even in undried state as well as dried state. CONSTITUTION:The objective ink can be produced by dispersing or dissolving a pigment and a releasing material in an aqueous vehicle free from volatile organic solvent or containing only a small amount of volatile organic solvent. The releasing material is a combination of silicone powder with a compound selected from water-soluble ester compound and polyether-modified silicone oil.

Description

[Detailed description of the invention]

0001

[Industrial Field of Application] Many inks based on volatile organic solvents have been proposed for marking inks for writing boards, but all of these have problems with odor and safety during use. In order to solve these problems, water-based inks have been proposed in recent years (for example, Japanese Patent Laid-Open Nos. 1-11174, 174577, 188576).
JP-A-2-117975, JP-A-2-117975, JP-A No. 124985, etc.), but these water-based inks have a common feature that the handwriting written on the ink-impermeable writing board surface is treated with the above-mentioned volatile organic solvent-based ink. It dries more slowly than ink handwriting, and is often wiped off before it dries, causing the problem that the ink spreads over the board surface and contaminates it. In addition, measures have been taken to add volatile organic solvents such as ethyl alcohol to speed up the drying of ink, but in reality, sufficient effects cannot be obtained unless they are added in a considerable amount (20 to 30% by weight or more). However, this leaves problems with safety, which is the main purpose of water-based inks.

0002

Problems to be Solved by the Invention The present invention is an aqueous-based ink in which all or most of the liquid component is water and has no substantial flash point, and when written on the surface of a writing board,
It is an object of the present invention to provide a water-based marking pen ink for a writing board that gives handwriting that can be easily and cleanly wiped off with a dry erasing material such as cloth or soft paper, not only immediately after drying but also in an undried state and after a period of time. be.

0003

[Means for Solving the Problems] The marking pen ink for writing boards of the present invention has a pigment and a release agent dispersed or dissolved in an aqueous vehicle, and the release agent comprises (A) dicarboxylic acid and polyalkylene glycol monomer. It is a combination of one or more compounds selected from diesters of alkyl ethers, esters of fatty acids and polyalkylene glycol monoalkyl ethers, diesters of polyalkylene glycols and fatty acids, polyether-modified silicone oils, and (B) silicone powder.

[0004] The above-mentioned pigments are generally pigments used in marking inks and printing inks, and specifically include azo-based, anthraquinone-based, condensed polyazo-based, thioindigo-based, metal complex salt-based, phthalocyanine-based, perinone/perylene-based, Organic pigments such as dioxazine and quinacridone,
Examples include inorganic pigments such as carbon black and iron oxide, and the amount is 0.5 to 20% by weight, preferably 1 to 1% by weight in the ink composition.
It is used in a range of 0% by weight.

[0005] Regarding the compounds listed in Group A of the above release agents (hereinafter referred to as release agent A), each release agent A
Explain the components that make up the.

Examples of dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid,
Azelaic acid, sebacic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, docosanedioic acid, fumaric acid,
Examples include maleic acid, malic acid, tartaric acid, and phthalic acid.

[0007] Fatty acids include caproic acid, caprylic acid,
Capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid,
Examples include oleic acid, erucic acid, linoleic acid, linoleic acid, ricinoleic acid, isocapric acid, isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, isoaracic acid, and oxystearic acid.

Examples of polyalkylene glycols include polyethylene glycol and polypropylene glycol, and examples of their monoethers include methyl, ethyl, propyl or butyl ether.

[0009] Polyether-modified silicone oil is a type of hydrophilic silicone oil in which some of the methyl groups of polydimethylsiloxane are substituted with polyoxyalkylene groups.

[0010] The release agent A is present in the ink composition in an amount of 0.5 to 2
It is used in an amount of 0% by weight, preferably in the range of 2 to 10% by weight.

The silicone powder of release agent B is selected from silicone resin powder, silicone elastomer powder, and powder obtained by supporting silicone oil in high concentration on an inorganic carrier. The silicone powder is 0.1 to 30% by weight in the ink composition, preferably 0.5% by weight.
It is used in a range of 10 to 10% by weight.

The aqueous vehicle consists of water and a water-soluble resin and/or surfactant for dispersing the pigment or silicone powder in the water. Examples of the water-soluble resin include polyvinylpyrrolidone, partially saponified polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, water-soluble acrylic resin, water-soluble cellulose derivative, gum arabic, etc., and the amount of these resins is 0.1 to 20% by weight in the ink composition. %,
It is preferably used in a range of 0.5 to 10% by weight. Examples of the surfactant include nonionic, anionic or cationic surfactants commonly used for pigment dispersion, polymer surfactants, fluorine surfactants, etc., and the amount thereof is 0.01 to 10% by weight in the ink composition. , preferably 0.1 to 3
It is used in a range of % by weight. As other additives, small amounts of lower alcohols such as ethanol and propanol, preservatives, rust preventives, antifoaming agents, pH regulators, etc. may be used as necessary.

[0013]

[Example] Table 1 shows the composition of the example ink.

[Table 1] The composition values in the table are expressed in parts by weight, and the contents of the raw materials are described below according to the note numbers. (All percentage values are weight %) 1. Water-based paste containing 20% carbon black, 6% polyvinyl alcohol 2. Water-based paste containing 10% Indanthrone Blue (C.I. Pigment Blue 60), 3% polyvinyl alcohol Paste 3. Aqueous paste containing 20% Lake Red C (C.I. Pigment Red 53:1), 7% polyvinyl alcohol 4.20% carbon black, 8% nonionic surfactant (polyoxyethylene nonylphenyl ether) ,2
5. Aqueous paste containing % anionic surfactant. Silicone elastomer powder (spherical, particle size distribution 1.0~
2.1 μm) 6. Silicone resin powder (Tospar 120; Toshiba Silicone Corporation) 7.8% silicone resin powder aqueous dispersion (X-5
2-660; Shin-Etsu Chemical Co., Ltd.) 8. Powder in which silicone oil 12500CS is supported on an inorganic carrier (Trefil F-250; Toray Dow Corning Silicone Co., Ltd.) 9. Silicone resin powder (spherical, particle size distribution 0.
3-0.7 μm) 10. Adipic acid triethylene glycol monomethyl ether diester 11. Oleic acid triethylene glycol monobutyl ether ester 12. Isocaprylic diester of polyethylene glycol 400 13. Polyether modified silicone oil (L-760
2; Nippon Unicar Co., Ltd.) 14. Polyoxyethylene alkyl phenyl ether 1
5. Phosphoric acid ester of polyoxyethylene alkylphenyl ether16. Polycarboxylic acid type polymer activator (Demol EP;
Kao Corporation) 17. Fluorine surfactant (Surflon S-141; Asahi Glass Co., Ltd.) 18. Partially saponified polyvinyl acetate (SMR-10M
; Shin-Etsu Chemical Co., Ltd.) 19. Hydroxypropyl cellulose (HPC-L; Nippon Soda Co., Ltd.)

[0014] Each example ink was prepared according to the following formulation. Example 1 A predetermined amount of resin and water are mixed and stirred with a stirrer until the resin is dissolved. Next, silicone powder and surfactant are added and processed in a sand mill for 1 hour. Thereafter, the pigment paste was added, mixed, and stirred with a disper for 1 hour. Additives were further added and stirring was continued for 1 hour to obtain a sample ink. Example 2 A predetermined amount of silicone powder, surfactant and water were mixed and processed in a sand mill for 1 hour to obtain a dispersion. A pigment paste was added to this dispersion, and the mixture was stirred for 1 hour with a disper, and then additives were added and stirred for another 1 hour to obtain a sample ink. Example 3 All components were mixed and stirred with a disper for 1 hour to obtain a sample ink. Examples 4 and 5 Inks were prepared according to the ink formulation of Example 1.

Three prior art water-based inks were then prepared as comparative inks for comparative test samples. Comparative Example 1 Ink with a composition obtained by removing silicone powder from the ink composition of Example 1 (ink described in JP-A-2-117975) Comparative Example 2 Ink containing polyether-modified silicone oil and water-insoluble inorganic powder as a release agent (Unexamined Japanese Patent Publication No. 1-188576
(Example 4 ink described in the above publication, except that 10 parts of a 25% quinacridone pigment aqueous dispersion was used instead of Ractimin Color Black as the water-dispersed pigment) Comparative Example 3 Polyether-modified silicone oil and non-polyester as a release agent were used. Ink containing water-soluble inorganic powder (JP-A-2-124985
(Example 1 ink described in the publication, except that 10 parts of a 20% Thren Blue aqueous dispersion was used instead of Ractimin Color Scarlet as the water-dispersible pigment.) Each ink was prepared according to the description in the respective publication.

Performance of sample ink (erasability of handwriting on writing board surface) Test Each sample ink was filled into a marking pen, a predetermined line was drawn on the enamel writing board surface, and the test was carried out in an undried state, immediately after drying, and after one week of aging. The subsequent erasability was investigated. For erasing, the erased state was observed after rubbing 5 times with a dry cloth under a load of 100 g. The test results are shown in Table 2.

[Table 2] The evaluation symbols in the table are as follows. Erasability of undried handwriting ○ Almost completely erased △ The board surface is slightly contaminated × Erasability of dry handwriting with significant contamination of the board surface ○ Almost completely erased △ A little bit on the board surface traces remain

[0017]

Effects of the Invention The handwriting on the writing board surface made with the water-based marking pen ink of the present invention does not contaminate the board surface, probably due to the excellent lubricating effect of the silicone powder that is movable in the handwriting even when wiped in an undried state. It can be wiped clean by rubbing with a dry eraser without any scratches. Also, the release agent A, which is present in the handwriting and inhibits the adhesion of the handwriting to the board surface,
Due to this action, handwriting that has dried on the board surface for a long time can be easily erased by rubbing with the dry erasing material. In this way, while maintaining the erasability of dry handwriting that has been required of writing board inks, when the undried handwriting on the writing board surface, which is seen with conventional water-based inks, is rubbed with an erasing material, The problem of contamination of the board surface has been resolved.

Claims (1)

[Claims] 1. A marking pen ink for a writing board comprising a pigment and a release agent dispersed or dissolved in an aqueous vehicle, wherein the release agent comprises (A) a diester of a dicarboxylic acid and a polyalkylene glycol monoalkyl ether;
A writing board characterized by being a combination of one or more compounds selected from esters of fatty acids and polyalkylene glycol monoalkyl ethers, diesters of polyalkylene glycols and fatty acids, polyether-modified silicone oils, and (B) silicone powder. Water-based marking pen ink.